Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/14—Styryl dyes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
  • A61K8/4933—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having sulfur as an exocyclic substituent, e.g. pyridinethione
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
  • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/14—Styryl dyes
  • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B49/00—Sulfur dyes
  • C09B49/12—Sulfur dyes from other compounds, e.g. other heterocyclic compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/42—Colour properties
  • A61K2800/43—Pigments; Dyes
  • A61K2800/432—Direct dyes
  • A61K2800/4322—Direct dyes in preparations for temporarily coloring the hair further containing an oxidizing agent
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/42—Colour properties
  • A61K2800/43—Pigments; Dyes
  • A61K2800/434—Luminescent, Fluorescent; Optical brighteners; Photosensitizers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
  • A61K2800/88—Two- or multipart kits

Definitions

• This invention relates to the dyeing of keratin materials using fluorescent thiol / disulfide dyes comprising one or more amino groups.
• the direct dyes which are conventionally used are, for example, dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triaryl methane type.
• the colorings that result from the use of direct dyes are temporary or semi-permanent dyes because the nature of the interactions that bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible their low dyeing power and their poor resistance to washes or perspiration.
• a chemical bleaching process consists in treating keratin materials such as keratinous fibers, in particular the hair, by a strong oxidizing system, generally consisting of hydrogen peroxide associated or not with persalts, most often in an alkaline medium.
• This bleaching system has the drawback of degrading keratin materials, in particular keratinous fibers, especially human fibers such as the hair, and of altering their cosmetic properties. Fibers indeed tend to become rough, more difficult to disentangle and more fragile. Finally, the lightening or the bleaching of keratinous fibers by oxidizing agents is incompatible with the treatments for modifying the shape of said fibers, particularly in the straightening treatments.
• Another lightening technique consists in applying fluorescent direct dyes to dark hair. This technique described in particular in the documents FR 2830189 and WO 2004/091473 makes it possible to respect the quality of the keratinous fiber during the treatment, but the fluorescent dyes employed do not exhibit satisfactory resistance to shampooing.
• direct dyes To increase the tenacity of the direct dyes, it is known to fix direct dyes by covalent bonding to the hair. For example, it is known to react dyes with reactive groups with the residues of cystine or cysteine very numerous in keratin fibers, see for example Journal of the Society of Dyers and Colourists, Guise and Stapleton, 91., 259-264 (1975); Journal of Cosmetic Chemistry, 42, 1-17 (1991); CA 2024509;
• the object of the present invention is to provide novel systems for dyeing keratin materials, in particular human keratinous fibers, in particular the hair, which do not have the drawbacks of existing bleaching processes.
• one of the aims of the present invention is to provide direct dyeing systems which make it possible to obtain lightening effects, in particular on naturally or artificially dark keratin fibers, which are stubborn in the face of successive shampoos, which do not degrade the fibers. keratinous and which do not alter their cosmetic properties.
• the present invention relates to a process for dyeing keratin materials, in particular keratinous fibers, in particular human fibers such as the hair, more particularly the dark hair, consisting in applying to the keratin materials a dye composition.
• a dye composition comprising, in a suitable cosmetic medium, at least one fluorescent dye thiol, chosen from the following dyes of formulas (I) and (II):
• R and R ' which may be identical or different, represent a hydroxyl group, an amino group (NR a R b ) or ammonium group (N + R a R b R c ), An " ; with R a , R b and R c , identical or different, representing a hydrogen atom or a group (C r C 4 ) alkyl; or else two alkyl groups R a and R b of the amino or ammonium group form a heterocycle comprising from 5 to 7 ring members and optionally comprising another heteroatom which is identical to or different from that of the nitrogen atom such as morpholinyl, piperazinyl, piperidinyl, pyrrolyl, morpholinium, piperazinium, piperidinium, pyrrolinium, and An " representing an anionic counterion;
• R 'and R " identical or different, represent a hydrogen atom or a group as defined for R and R'" respectively;
• R 'g, R "g, R” g, R h, R' h, R “h and R” 'h, identical or different, represent a hydrogen, halogen, a group amino, (di) (CrC 4 ) alkylamino, cyano, carboxy, hydroxy, trifluoromethyl, acylamino, alkoxy -C 4 (poly) hydroxyalkoxy, C 2 -C 4, (Ci-C 4) alkylcarbonyloxy, (Ci-C 4) alkoxycarbonyl, (CrC 4) alkylcarbonylamino, acylamino, carbamoyl, (C 1 -C 4 ) alkylsulfonylamino, an aminosulfonyl radical, or a (C 1 -C 6 ) alkyl radical optionally substituted with a group chosen from (C 1 -C 2 ) alkoxy, hydroxy, cyano, carboxy, amino, (
• R'i, R “i, R” and R “" i identical or different, represent a hydrogen atom, or a group (C r C 4 ) alkyl; particularly R'j, R ", R '", and R "" i represents a hydrogen atom;
• n, m ' identical or different, represent an integer inclusive between 1 and 10; especially an integer inclusive between 2 and 4; preferentially m and m 'are 2;
• Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline earth metal; iv) an ammonium group: N + R ⁇ R ⁇ R ⁇ R ⁇ or a phosphonium group: P + R ⁇ R ⁇ R ⁇ R ⁇ with R ⁇ , R ⁇ , R ⁇ and R ⁇ , identical or different, representing a hydrogen atom or a (dC 4 ) alkyl group; or v) a thiol protecting group; Being heard that :
• Another subject of the invention is a dyeing composition
• a dyeing composition comprising, in a suitable cosmetic medium, at least one fluorescent dye of formula (I) or (II) as defined above, and a reducing agent.
• the subject of the invention is also new fluorescent dyes of formula (I) or (II) as defined above.
• the dyeing process according to the invention makes it possible to visibly stain dark keratin materials, in particular dark human keratin fibers, especially dark hair.
• the process of the invention makes it possible to obtain a coloration of the keratin materials, in particular human keratinous fibers, in particular the hair, without degrading said material, which is persistent with respect to shampoos, of the common aggressions (sun, perspiration). , and other hair treatments.
• the process of the invention also makes it possible to obtain a lightening of keratin materials such as keratinous fibers, particularly dark keratinous fibers and more particularly dark hair.
• the term naturally or artificially dark hair hair whose pitch is less than or equal to 6 (dark blonde) and preferably less than or equal to 4 (chestnut).
• the lightening of the hair is evaluated by the variation of "pitch" before and after application of the compound of formula (I) or (II).
• tone is based on the classification of natural nuances, a tone separating each nuance from that which follows or immediately precedes it. This definition and the classification of natural shades is well known to professionals in the hair and published in the book “Science of hair treatment” Charles ZVIAK 1988, Ed Masson, p. 215 and 278.
• Heights range from 1 (black) to 10 (very light blond), a unit corresponding to a tone; the higher the number, the clearer the nuance.
• An artificially colored hair is a hair whose color has been modified by a coloring treatment, for example a coloration with direct dyes or oxidation dyes.
• the composition must, after application to hair, for example chestnut, bring to the results below.
• the reflectance curves are then compared as a function of the wavelength, of the hair treated with the composition of the invention and of the untreated hair.
• the curve corresponding to the treated hair should show a reflectance in the wavelength range of 500 to 700 nanometers higher than the curve corresponding to untreated hair.
• the wavelength where the difference is greatest between the reflectance curve of the treated hair and that of the untreated hair is in the wavelength range of 500 to 650 nanometers, and preferably in the the wavelength range from 550 to 620 nanometers.
• the wavelength range 500 to 650 nanometers, and preferably in the the wavelength range from 550 to 620 nanometers.
• the "aryl” or “heteroaryl” radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent carried by a carbon atom, chosen from: • a Ci-Ci 6 alkyl radical, preferably in C 1 -C 8 , optionally substituted with one or more radicals selected from hydroxyl, C 1 -C 4 alkoxy radicals;
• 5- to 7-membered preferably 5- or 6-membered, optionally substituted saturated or unsaturated group optionally comprising another heteroatom identical to or different from nitrogen;
• a halogen atom such as chlorine, fluorine or bromine; . a hydroxy group;
• a 5- or 6-membered optionally cationic heteroaryl radical preferentially imidazolium, and optionally substituted with a (C 1 -C 4 ) alkyl radical, preferably methyl;
• An amino radical substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: i) a hydroxyl group, ii) an amino group optionally substituted by one or two C 1 -C alkyl radicals 1- C 3 optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom, different or different from 'nitrogen,
• radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C 1 -C alkyl radical; 2 ;
• (R) 2 N-CO- in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group;
• R 1 SO 2 -NR- in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C 1 alkyl radical; -C 4 , a phenyl radical;
• R radicals which may be identical or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group,
• a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or unsubstituted);
• a cyano group • a cyano group; a polyhaloalkyl group comprising from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which are identical or different, the polyhaloalkyl group is, for example, trifluoromethyl;
• cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom chosen from the groups: hydroxy,
• RCO-NR'- in which the radical R 'is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the R radical is a C 1 -C 2 alkyl, amino radical; substituted with two identical or different C 1 -C 4 alkyl groups optionally bearing at least one hydroxyl group;
• RCO-O- wherein the radical R is a C 1 -C 4 alkyl radical substituted by one or two identical or different C 4 -C 4 alkyl groups optionally bearing at least one hydroxyl group, said alkyl radicals being capable of forming with 1 the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or different from nitrogen;
• an "aryl” radical represents a mono or polycyclic group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;
• a "diarylalkyl” radical represents a group comprising, on the same carbon atom of an alkyl group, two identical or different aryl groups, such as diphenylmethyl or 1,1-diphenylethyl;
• a "heteroaryl radical” represents an optionally cationic mono or polycyclic group, optionally cationic, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium, and of which at least one ring is aromatic; preferably heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyle, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinoly
• a "diheteroarylalkyl” radical represents a group comprising, on the same carbon atom of an alkyl group, two heteroaryl groups, identical or different, such as difurylmethyl, 1,1-difurylethyl, dipyrrolylmethyl, dithienylmethyl;
• cyclic radical is a non-aromatic, mono or polycyclic cycloalkyl radical, condensed or not, containing from 5 to 22 carbon atoms, which may contain from 1 to several unsaturations; particularly the cyclic radical is cyclohexyl;
• cyclic sterically hindered radical is a cyclic radical, aromatic or not, substituted or unsubstituted, hindered by steric effect or constraint, comprising from 6 to 14 members, which can be bridged, as sterically hindered radicals, mention may be made of bicyclo [1.1.0] butane, mesytyls such as 1,3,5-trimethylphenyl, 1,3,5-triterbutylphenyl, 1,3,5-isobutylphenyl, 1,3,5-trimethylsillylphenyl and adamantyl ;
• heterocyclic radical or heterocycle is a mono- or polycyclic non-condensed radical, condensed or not, containing from 5 to 22 members, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium;
• an “alkyl radical” is a linear or branched C 1 -C 6 hydrocarbon-based radical, preferably C 1 -C 5 ;
• alkyl radical may be substituted by one or more radicals chosen from radicals i) hydroxy, ii) C 1 -C 4 alkoxy, Ni) acylamino, iv) amino optionally substituted with one or two identical or different C 1 -C 4 alkyl radicals, said alkyl radicals being able to form with the nitrogen atom which carry a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom different or different from nitrogen; v) or a quaternary ammonium group
• R'R "R '" M " for which R', R", R '", which are identical or different, represent a
• an "alkoxy radical” is an alkyl-oxy or alkyl-O- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in C 1 -C 16 preferentially;
• an "alkylthio radical” is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, C 1 -C 16 preferentially d-Cs; when the alkylthio group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above; the boundaries delimiting the range of a range of values lie within this range of values; an "organic or inorganic acid salt” is more particularly chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4 , iv) from alkylsulfonic acids: Alk-S (O) 2 OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2 OH such as benzene sulfonic acid and toluene sulfonic acid;
• the fluorescent dyes of formula (I) or (II) are compounds capable of absorbing in UV or visible radiation at a wavelength ⁇ abs of between 250 and 800 nm and capable of reemitting in the visible range at a emission wavelength ⁇ em between 400 and 800 nm.
• the thiol fluorescent compounds of the invention are dyes capable of absorbing in the visible ⁇ abs between 400 and 800 nm and reemitting in the visible ⁇ em between 400 and 800 nm.
• the fluorescent dyes of formula (I) or (II) are dyes capable of absorbing at an abs ⁇ between 420 nm and 550 nm and reemitting in the visible at an ⁇ em between 470 and 600 nm.
• the fluorescent compounds of formula (II) of the invention contain a SY function which can be in the covalent -SY or ionic -S " Y + form depending on the nature of Y and the pH of the medium.
• One particular embodiment relates to thiols fluorescent dyes having a group of formula (II) with a SY function, where Y represents a hydrogen atom or an alkali metal.
• Y represents a hydrogen atom.
• Y is a protective group known to those skilled in the art such as those described in the books “Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981, pp.193-217;
• Y represents a protective group of the thiol function
• Y is chosen from the following radicals: (C 1 -C 4 ) alkylcarbonyl;
• Arylcarbonyl as phenylcarbonyl
• Aryloxycarbonyl • aryl (CrC 4 ) alkoxycarbonyl;
• aryl such as phenyl, dibenzosuberyl, or 1,3,5-cycloheptatrienyl
• Optionally substituted heteroaryl including in particular cationic or non-cationic heteroaryl, comprising from 1 to 4 following heteroatoms: i) monocyclic with 5, 6 or 7 members such as furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl, isoxazolium thiazolyl, thiazolium, isothiazolyl, isothiazolium, 1,2,4-triazolyl, 1,2,4-triazolium, 1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl, 1 , 2,4-oxazolium, 1,2,4-thiadiazolyl, 1,2,4-thiadiazolium, pyrylium, thiopyridyl, pyridinium, pyrimidinyl, pyrimidinium, pyrazinyl,
• the two rings A, ⁇ optionally comprise a heteroatom
• the ring B is a 5-, 6- or 7-membered, particularly 6-membered ring and contains at least one heteroatom such as pyperidyl, pyranyl
• optionally substituted heterocycloalkyl, optionally cationic heterocycloalkyl represents in particular a saturated or partially saturated 5, 6 or 7 membered monocyclic group comprising 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen, such as di / tetrahydrofuranyl; , di / tetrahydrothiophenyl, di / tetrahydropyrrolyl, di / tetrahydropyranyl, di / tetra / hexahydrothiopyranyl, dihydropyridyl, piperazinyl, piperidinyl, tetramethylpiperidinyl, morpholinyl, di / tetra / hexahydro
• aryl (CrC 4 ) alkyl such as 9-anthracenylmethyl, phenylmethyl or diphenylmethyl optionally substituted by one or more groups chosen in particular from (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, such as methoxy, hydroxy, (C 1 -C 4 ) alkylcarbonyl, (di) (C 1 -C 4 ) (alkyl) amino such as dimethylamino;
• heteroaryl (C r C 4 ) optionally substituted alkyl the heteroaryl group is in particular, cationic or non-monocyclic, comprising 5 or 6 members and 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur , such as pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium, triazinyl, optionally substituted with one or more group such as alkyl particularly methyl preferably (di) heteroaryl (CrC 4 ) alkyl is (di) heteroarylmethyl or (di) heteroarylethyl;
• aryl such as phenyl optionally substituted with one or more groups such as (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, hydroxy;
• heteroaryl such as thiophenyl, furanyl, pyrrolyl, pyranyl, pyridyl, optionally substituted with a group (C 1 -00aIkVIe;
• R ' 1 R 12 R' 3 with R ' 1 , and R' 2 identical or different represent a hydroxyl group, (C 1 -C 4 ) alkyl or alkyl, R ' 3 represents a hydroxyl group or C r C 4 ) alkoxy, and Z 1 represents an oxygen or sulfur atom;
• Sterically hindered cyclic such as the adamantyl group
• Optionally substituted alkoxy (CrC 4 ) alkyl such as methoxy methyl (MOM), ethoxyethyl (EOM) and isobutoxymethyl.
• the protected thiol fluorescent dyes of formula (II) contain a cationic aromatic 5- or 6-membered monocyclic heterocyclic group Y 1) comprising 1 to 4 heteroatoms chosen from oxygen, sulfur and nitrogen. , such as oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium, pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium, tetrazinium, oxazepinium, thiepinyl, thiepinium, imidazolium; ii) cationic 8 to 11-membered bicyclic heteroaryl such as indolinium, benzoimidazolium, benzoxazolium, benzothiazolium,
• R ' c and R' d identical or different, represent a hydrogen atom or a group (dC 4 ) alkyl; preferentially R ' c to R' d represent a grouping
• Y represents a group chosen from oxazolium, isoxazolium, thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium, 1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium , pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium, benzoimidazolium, benzoxazolium, benzothiazolium, these groups being optionally substituted by one or more (CrC 4 ) alkyl groups including methyl.
• Y represents an alkali metal or a protective group such as:
• (C r C 4 ) alkylcarbonyl such as methylcarbonyl or ethylcarbonyl
• arylcarbonyl such as phenylcarbonyl
• aryl such as phenyl
• monocyclic 5- or 6-membered heteroaryl such as imidazolyl or pyridyl
• Cationic monocyclic 5- to 6-membered heteroaryl such as pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium, triazinium, imidazolium; these groups being optionally substituted by one or more, identical or different, (C 1 -C 4 ) alkyl groups such as methyl; 8 to 11-membered cationic bicyclic heteroaryl such as benzoimidazolium, or benzoxazolium; these groups being optionally substituted by one or more, identical or different, (dC 4 ) alkyl groups such as methyl;
• the dyes of the invention belong to the formula (Ia) or (Ma) which have an ethylene group connecting the pyridinium part to the phenyl in the ortho or para position of the pyridinium or in 2-4 ', 4-2', 4- 4 ':
• R hj R " h are ortho of the pyridinium group and R ' h , R" h represent a hydrogen atom.
• Another aspect of the invention relates to the dyes of formula (Ia) or (Ma) having groups R 9 , R " g at the 3 'position and R' g / R" g which represent a hydrogen atom.
• the dyes of formula (Ia) and (Ma) have their amino group: R '(CH 2 ) p -N- (CH 2 ) q -R and / or R "(CH 2 ) p. -N- (CH 2 ) 2 ) q. -R '"in the position l'.
• thiol fluorescent dyes By way of example of thiol fluorescent dyes, mention may be made in particular of the following compounds:
• Protected thiol dyes of formula (M ') can be synthesized in two stages.
• the second step of protecting the function thiol according to conventional methods known to those skilled in the art to lead to protected thiol dyes of formula (H ').
• thiol fluorescent dyes of formula (HH) by reduction of a fluorescent dye to two chromophores, bearing a disulfide function -SS- (I ') and ii) to protect, according to conventional methods, said thiol function of (MH) with the reagent 7 Y'R to access the protected thiol fluorescent dyes of formula (M ').
• the thiol compound 6 may also be metallized with an alkali metal or alkaline earth metal Met * to yield the thiolate fluorescent dye of formula (M ").
• Met * represents an alkali metal or an alkaline earth metal, particularly sodium or potassium, it being understood that when the metal is an alkaline earth metal 2 thiolate-functional chromophores-S " may be associated with 1 Metal 2+ ;
• Y' represents a protecting group of thiol function;
• R of Y'R represents a leaving group nucleofuge, such as, for example, mesylate, tosylate, triflate or halide.
• thiol reactant Y'-SH comprising a group Y 'as defined previously, the nucleophilic function SH of which can react on the carbon atom in alpha of the halogen atom carried by the fluorescent chromophore (a). to lead to the protected thiol fluorescent dye of formula (H '):
• R, R ', R 9, R' g, R hj R 'hj R'j, R ", m, p, q, and M' (M ') are as defined above, and Hal represents an atom of nucleofugal halogen such as bromine, iodine or chlorine.
• R, R ', R 9, R' g, R h, R'H, R ', R ", m, p, q, and M' are as defined above.
• a variant is to use the halide site comprising the fluorescent chromophore (a) a chromophore comprising another type of nucleofuge such as tosylate, mesylate.
• a compound containing a protected thiol group contains a leaving group R, such as, for example, mesylate, tosylate, or triflate, which can undergo the nucleophilic attack of the amine carried by the styryl fluorescent chromophore:
• halides as nucleofugal leaving group on a thiol compound which may be substituted by a primary amine function, for example carried by a styryl fluorescent chromophore:
• the thiol fluorescent dyes of formula (II) according to the invention can be obtained by reaction of a compound comprising a thiol group Y as defined above and an electrophilic group (f) with a pyridinium compound comprising a nucleophilic group.
• a compound comprising a thiol group Y as defined above and an electrophilic group (f) with a pyridinium compound comprising a nucleophilic group.
• This reaction is commonly known as "Knoevenagel” condensation.
• activated methylenes is meant those which preferentially contain, in position 2 or 4 of the pyridinium group, a methylene group Rj
• the thiol fluorescent dyes formed can be converted to protected thiol stain -SY 'by protecting the thiol -SH using conventional protecting groups.
• the thiol fluorescent dyes are metallated by also using the conventional methods known in the art such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4 èm ⁇ Ed, John Wiley & Sons, NY , 1992.
• Protected thiol dyes may be deprotected by conventional routes such as those described in the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981; "Protecting Groups", P. Kocienski, Thieme, 3rd ed., 2005.
• the starting reagents are commercial or accessible by conventional methods known to those skilled in the art.
• Gp representing a leaving group nucleofuge, such as mesylate, tosylate, triflate or halide.
• the Gp-counter-ions of the compounds (I '), above, may be replaced by other M' counter-ions from methods known to those skilled in the art, in particular by ion-exchange resin.
• the disymmetrical disulfide dyes of formula (I) may be synthesized in one step by reacting an unprotected thiol fluorescent dye with a Y'-protected thiol fluorescent dye to form the disulfide dye of formula (I).
• the thiol fluorescent dyes formed can be converted to protected thiol stain -SY 'by protecting the thiol -SH using conventional protecting groups.
• the thiol fluorescent dyes are metallated by also using the conventional methods known in the art such as those described in Advanced Organic Chemistry, "Reactions, Mechanisms and Structures", J. March, 4 èm ⁇ Ed, John Wiley & Sons, NY , 1992.
• Protected thiol dyes can be deprotected by conventional routes such as those described in the "Protective Groups in Organic Synthesis", TW Greene, John Willey & Sons ed., NY, 1981; "Protecting Groups", P. Kocienski, Thieme, 3 èm ⁇ ed. 2005.
• composition of the invention contains at least one fluorescent dye of formula (I) or (II).
• composition of the invention may also contain a reducing agent.
• This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol.
• thiols for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid and its esters, especially the glycerol monothioglycolate, and thioglycerol.
• This reducing agent may also be chosen from borohydrides and their derivatives, for example the salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxyborohydride: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra n-butylammonium, benzyltriethylammonium); catechol borane.
• borohydrides and their derivatives for example the salts of borohydride, cyanoborohydride, triacetoxyborohydride, trimethoxyborohydride: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra n-butylammonium, benzyltriethylammonium); catechol borane.
• the dye composition useful in the invention generally contains a quantity of fluorescent dye of formula (I) or (II) of between 0.001 and 50% relative to the total weight of the composition. Preferably, this quantity is between
• the dye composition may further contain additional direct dyes.
• These direct dyes are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.
• the dye composition may contain one or more oxidation bases and / or one or more couplers conventionally used for dyeing keratinous fibers.
• oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.
• couplers there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.
• the coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.
• the oxidation base (s) present in the dyeing composition are generally present each in an amount of between 0.001% and 10% by weight of the weight. total of the dyeing composition, preferably between 0.005 and 6% by weight.
• addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
• an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates
• a base such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
• the medium suitable for dyeing is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent.
• organic solvent there may be mentioned, for example lower alkanols dC 4 , such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
• the solvents when present are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.
• the invention contains a reducing agent capable of reducing the disulfide bonds of keratin and / or of the dye of formula (I).
• This reducing agent is as defined above.
• the dye composition may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers.
• adjuvants conventionally used in compositions for dyeing hair such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers.
• inorganic or organic thickeners and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as aminosilicones, film-forming agents, ceramides, preserving agents, opacifying agents, conductive polymers.
• conditioning agents such as, for example, volatile or non-volatile silicones, modified or otherwise, such as aminosilicones, film-forming agents, ceramides, preserving agents, opacifying agents, conductive polymers.
• the adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.
• the pH of the dyeing composition is generally between 3 and 14 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems.
• acidifying agents mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.
• alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula ( ⁇ ):
• R a4 R a3 ( ⁇ ) wherein W is a propylene residue optionally substituted with a hydroxy group or an alkyl radical Ci-C 4; R i, R a2, R a3 and R a4, identical or different, represent a hydrogen atom, an alkyl radical or C 4 -C 4 hydroxyalkyl.
• the dye composition may be in various forms, such as in the form of liquid, cream, gel, or in any other form suitable for dyeing keratinous fibers, and in particular hair.
• a reducing agent may be applied pre-treatment before the application of the composition containing at least one fluorescent dye of formula (I) or (II).
• This reducing agent may be chosen from thiols, for example cysteine, homocysteine, thiolactic acid, the salts of these thiols, phosphines, bisulfite, sulphites, thioglycolic acid, and its esters, in particular glycerol monothioglycolate, and thioglycerol.
• This reducing agent may also be chosen from borohydrides and their derivatives, such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catecholborane.
• borohydrides and their derivatives such as, for example, borohydride, cyanoborohydride, triacetoxyborohydride or trimethoxyborohydride salts: sodium, lithium, potassium, calcium, quaternary ammonium salts (tetramethylammonium, tetraethylammonium, tetra butylammonium, benzyltriethylammonium); catecholborane.
• This pretreatment may be of short duration, in particular from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes with a reducing agent as mentioned above.
• the composition comprising at least one fluorescent dye of formula (I) or (II) also contains at least one reducing agent as defined above. This composition is then applied to the hair.
• the process of the invention may be preceded by a deprotection step aimed at rendering the SH function in situ.
• the deprotection step can also be carried out in the course of a hair pretreatment step such as, for example, the reducing pretreatment of hair.
• the reducing agent is added to the dyeing composition containing at least one fluorescent dye of formula (I) or (II) at the time of use.
• the composition comprising at least one fluorescent dye of formula (I) or (II) also contains at least one reducing agent as defined above. This composition is then applied to the hair.
• the reducing agent is applied in post-treatment, after the application of the composition containing at least one fluorescent dye of formula (I) or (II).
• the duration of the post-treatment with the reducing agent may be short, for example from 0.1 second to 30 minutes, preferably from 1 minute to 15 minutes, with a reducing agent as described above.
• the reducing agent is a thiol or borohydride type agent as described above.
• a particular embodiment of the invention relates to a method in which the fluorescent dye of formula (I) or (II) can be applied directly to hair without reducing agents, free of pre or post-treatment reducers.
• a treatment with an oxidizing agent may optionally be associated.
• Any type of conventional oxidizing agent may be used in the art. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, as well as the enzymes among which may be mentioned peroxidases, oxides, 2-electron reductases such as uricases and 4-electron oxygenases such as laccases.
• This oxidizing agent may be applied to the fibers before or after the application of the composition containing at least one fluorescent dye of formula (I) or (II).
• the application of the dye composition according to the invention is generally carried out at room temperature. It may, however, be carried out at temperatures ranging from 20 to 180 ° C.
• the invention also relates to a multi-compartment device or "kit" for dyeing in which a first compartment contains a dye composition comprising at least one fluorescent dye.
• Formula (I) or (II) and a second compartment contains a reducing agent capable of reducing the disulfide functions of keratin materials.
• One of these compartments may further contain one or more other dyes of direct dye type or oxidation dye.
• a multi-compartment device in which a first compartment contains a dye composition comprising at least one fluorescent dye of formula (I) or (II); a second compartment contains a reducing agent capable of reducing the disulfide bond of the keratin materials; a third compartment contains an oxidizing agent.
• the dyeing device contains a first compartment containing a dye composition which comprises at least one protected thiol fluorescent dye of formula (II) and a second compartment containing an agent capable of deprotecting the protected thiol to release the thiol.
• Each of the above-mentioned devices may be equipped with means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2 586 913.
• the following examples serve to illustrate the invention without however to be limiting in nature.
• the thiol fluorescent dyes of the examples below have been fully characterized by conventional spectroscopic and spectrometric methods.
• the organic phases are extracted with 100 ml of ice water; 100 ml of water, with 3 times 50 ml of saturated NaHCO 3 solution and twice 20 ml of saturated NaCl, are then dried over anhydrous Na 2 SO 4 .
• L 1 AcOEt is evaporated and 17.49 g of pale yellow clear oil are recovered. The analyzes indicate that the product is compliant.
• Step 2 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (4-methylpyridinium) Dimethanesulfonate
• Step 3 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis [4 - ((E) -2- ⁇ 4- [bis (2-hydroxyethyl) amino] phenyl ⁇ vinyl) pyridinium dimethane sulfonate ] [1] 4.32 g of 4- [bis- (2-hydroxyethyl) amino] benzaldehyde, 10 ml of iPrOH, and 1.69 ml of pyrrolidine are mixed with stirring for 10 minutes. 1.18 mL of acetic acid is added and the mixture is stirred at room temperature for 20 minutes.
• Step 2 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis [4 - ((E) - 2- ⁇ 4- [ethyl (2-hydroxyethyl) amino] -2-methylphenyl ⁇ dibromide 1-methylvinyl) pyridinium] [2] 5 g of 4- [ethyl- (2-hydroxy-ethyl) -amino] -2-methyl-benzaldehyde, 10 ml of iPrOH, and 1.74 ml of pyrrolidine are mixed together under stirring for 10 min. 1.21 ml of acetic acid are added and the mixture is stirred at room temperature for 20 minutes.
• Step 2 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis [4 - ((E) -2- ⁇ 4 - [[3- (dimethylamino) propyl] (methyl) amino di methanesulfonate ] phenyl ⁇ vinyl) pyridinium] [3] 2 g of 4 - [(3-dimethylamino-propyl) -methylamino] benzaldehyde solubilized in 5 ml of iPrOH, to which 585 ⁇ l of pyrrolidine are stirred at room temperature. room temperature for 10 minutes.
• Step 1 Synthesis of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis (2-methyl-pyridinium) dibromide
• a mixture of 56 g of 1-bromo-2 - [(2-bromoethyl) disulfanyl] ethane and 15 ml of N-methylpyrrolidone (NMP) is added dropwise to 35 g of 2-picoline with stirring at 80 ° C. C.
• the mixture (white suspension) is stirred for 30 min at 80 ° C., 100 ml of ACN are added, stirring is maintained at 80 ° C. for 90 min.
• the solid obtained is filtered, washed with 100 ml of ACN and then dried. 56.2 g of brown powder are collected. 45 g of this powder are suspended in 300 ml of iPrOH at reflux.
• Step 2 Synthesis of 3 - [(4-formylphenyl) (methyl) amino] -N, N, N-trimethylpropan-1-aminium methylsulfate
• Step 3 Synthesis of the salt of 1,1 '- (disulfanediyldiethane-2,1-diyl) bis ⁇ 2 - [(E) -2- (4- ⁇ methyl [3- (trimethylammonio) propyl] amino ⁇ phenyl) vinyl ] pyridinium ⁇ [4] 0.62 g of 3 - [(4-formylphenyl) (methyl) amino] -N, N, N-trimethylpropan-1-aminium methyl sulfate solubilized in 2 mL of iPrOH and 3 mL of methanol, to which 0.15 ml of pyrrolidine are added, are stirred at ambient temperature for 10 minutes.
• UV diode array ⁇ 400-700nm
• compositions A (9 ml) and B (1 ml) are mixed, and then the mixture obtained is applied to a lock of 1 g of dark hair (pitch 4) for 30 minutes at room temperature. (The locks are returned and re-impregnated after 15 minutes).
• EXAMPLE 2 Method of Staining with the Compound [5] 10 ml of fresh solution of the compound [5] of the synthetic example are applied to a lock of 1 g of hair of pitch 4 arranged at the bottom of the same bowl for 30 minutes at room temperature (the locks are returned and re-impregnated after 15 minutes). The locks are then rinsed with running water and dried. After staining the wick of pitch 4 has become visually clearer than untreated control locks.
• the locks thus treated are divided in two, one half is subjected to 5 successive shampoos in a cycle which comprises wetting the locks with water, washing with a conventional shampoo, rinsing with water followed by drying.
• L *, a * and b * represent the measured values before staining and L 0 *, ao * and bo * represent the measured values before staining (or shampooing).
• compositions according to the invention were expressed as a function of the reflectance of the hair. These reflectances are compared to the reflectance of a lock of untreated HT4 pitch hair.
• the reflectance is measured using a KONIKA-MINOLTA®, CM 260Od spectrophotocolorimeter and after irradiation of the hair with visible light in the wavelength range of 400 to 700 nanometers. Reflectance of wicks treated with compounds 1 and 2 at application and after 5 shampoos

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